Hydroxylation of unsaturated halides



Patented Sept-'22, 1942 I NITED STATES PATENT oFFicE mnoxrna'rron or onsa'roaa'rsn Ludwig signer to Shell Francisco, Colin,

' 14 Claims.

for the direct hydroxylation of unsaturated organic halides theunsaturated carbon atoms of which are of aliphatic character and are devoid of halogen atoms. The invention is especially directed to a process whereby unsaturated monohalides containing an oleflnic linkage between two aliphatic carbon atoms devoid of halogen atoms may be readily and effectively converted into the corresponding dihydroxylated monohalogenated organic compounds. In its most specific embodiment, the invention provides a process ior producing dihydroxylated halides from allyl type unsaturated monohalides, that is, compounds containing an oleiinic linkage between .two carbon atoms of aliphatic character, one of which is directly linked to a saturated monohalogenated carbon atom of aliphatic character. The invention is of particular commercial value as applied to the manufacture of glycerol monochlorhydrin from allyl chloride, the monochlorhydrin being suitable for the production of glycerol.

The halogenated unsaturated hydrocarbons vwhich may be hydroxylated to the corresponding polyhydroxylated halogenated compounds in accordance with the process the invention are characterized by containing in their structure'an unsaturated linkage, which may be oleiinic or acetylenic, between two aliphatic carbon atoms devoid of any halogen atoms. halogen atom or atoms in these halogenated unsaturated hydrocarbons are attached to saturated carbon atoms which may be of primary, secondary or tertiary character. The halogen atom or atoms may also be attached to unsaturated carbon atoms; however, in such a case the halogenated unsaturated hydrocarbon should contain another unsaturated linkage between two aliphatic carbon atoms devoid of halogen atoms. The halogenated carbon atom in the defined class of unsaturated halogenated hydrocarbons may be part of an open alkenyl chainor it may be contained in a cycloalkenyl ring. Representative unsaturated halides. which may be hydroxylated to the correspondingv p lyhydroxylated halogenated organic compounds are allyl chloride, allyl.

bromide. crotyl chloride, crotyl bromide, methyl vinyl carbinyl chloride, vinyl carbinyl chloride, the allyl type isopentenyl chlorides, 4-chlor-butene-1, 5,-chlor-pentene-1,

5-chlor-pentene-2, i-chlor-pentene-Z, 3-chlor-1-- a process'ior the pro-* methallyl chloride, ethyl Bosemtein. San Francisco, Gall! as- Development Company. Ban 1 corporayon 0! Delaware Application January, 1941, Serial No. 876,836

(CL zoo-cs3) Preferably, the

. oxide to allyl chloride may be represented phenyl-propene-l, 4-chlor-1-phenyl-butene-1, 3- chlor 2 phenyl propene -l, l-chlor-cyclopentene-2, l-brom-cyclopentene 2, 4 methyl -l- 'chlor-cyclopentene-il, e-ethyl-l-chlor-cyclopentone-2, 1-chlor-cyclohexene-2, i-chlor-z-chlormethyl-propene-2, 1,1- dichlor 2 methyl-propene-2, 3-chlor-2,4-dimethyl-pentene-1, 2,5411! brom-hexene-3, 2,5-dimethyl 2,5 dibrom-hexens-3, 1,1-dichlor-butene-2, 1,4-dichlor-butene-2, 3,4-dichlor-butene-1, l,l-dibrom--2-met1 i7l-propane-2, 3.4-dibrom-2-methyl-butene-l, and the like, and their homologues and analogues, as well as suitable substitution products. Particularly suitable unsaturated halides are those which are o! the allyl type, that is halides possessing an oiefinic linkage between two carbon atoms 01 aliphatic character both of which are devoid oi halogen atoms and one or both or which are linked directly to a saturated halogenated (preierably monohalogenated) carbon atom of allphatic character. Allyl chloride, allyl bromide, crotyl chloride, crotyl bromide, isobutenyl chloride,' 1-ch1or-pentene-2, 3-chlor-cyclopentene-l,

and the like, and their homologues and analogues, are representative allyl type halides which may be hydroxylated according to this process to the corresponding dihydroxylated halogenated com pounds.

It has been found that the above-defined unsaturated halides may be converted to the corresponding halogenated polyhydroxylated compounds by subiecting the halides to the action 01 hydrogen peroxide. It also has been found that dihydroxylated'halogenated organic compounds may be readily and economically produced by reacting a mono-oleflnic halide devoid of halogen atoms on the unsaturated carbon atoms with hydrogen peroxide in the presence of a hydroxylation promoting catalyst, particularly one comprising an oxide of a metal which assumes varied valencies. Such a reaction eiiects the addition of a molecule of hydrogen peroxide to each molecule oi! the gmono-oleflnic halide, thus saturating the same-and producing the corresponding dihydroxylated" halide. For example, the catalytic addition of hydrogen perby the ioilowing formula:

class of such hydroxylation promoting catalysts includes substances comprising or consisting oi ation reaction.

also possible, and sometimes um tetroxide, vanadium pentoxide, chromium" troxide. Particularly good results have been obtained by effecting the reaction in the presence of osmium tetroxide. Because of the catalytic anhydride, molybdenum oxide and osmium teaction of the hydroxylating catalysts, such as the aforementioned metal oxides, the quantity of the catalyst employed may vary within relatively wide limits. Generally, relatively small amounts of such catalyst, e. g. from about 0.01% to about 0.1% by weight of the unsaturated halide treated, will be suflicient to promote the desired hydroxyl- However, the use of larger amounts of the catalyst is permissible and frequently desirable. The particular catalyst selected for the catalytic hydroxylation may be prepared and used in a variety of ways. Although the catalysts may be en iployeddn the form of solid granules, chip and the like,-it is preferable, to use them in the form ofsolutions or suspensions in various solvents. For example, it was found that osmium tetroxide may be employed in the formof its aqueous solution or by dissolving this oxide,

in the unsaturated halide before the latter is reacted with the hydrogen peroxide. In some instances, particularly when the reaction is to be effected in a continuous manner, the catalyst may be deposited or dispersed on an inert carrier, e. g. pumice, silicon, etc., which may then be disposed in the reaction chamber through which the reactants may be passed either continuously or otherwise. The hydroxylating'catalyst may also consist of a mixture of the above and other active reaction promoting substance, and/or may contain inert substances. 5

The reaction between the unsaturated halides and the hydrogen peroxide may be effected either in the presence or absence of water. When unsaturated halides which are substantially insoluble in water, such as allyl chloride, are to be hydroxylated, the water will act as a solvent and extracting agent for the halogenated dihydroxylated compound. Therefore, by eifecting the reaction in an aqueous medium, the dihydroxylated halogenated compound may be continuously or intermittently removed from the reaction mixture. Other solvents for the polyhydroxylated halo compounds may also be used.

The hydrogen peroxide may be introduced into the reaction zone either as such, or in solution with water or in a non-aqueous solvent which is preferably selected from such organic substances as do not undergo oxidation during the reaction. Saturated ethers and saturated nitriles may be cited as examples of such solvents, although saturated tertiary alcohols in general, and tertiary butyl and tertiary amyl alcohols in particular, are also among the solvents which are suitable for dissolving the hydrogen peroxide to be employed as the hydroxylating agent.

The reaction may be effectively realized .by intimately mixing the reactants and by maintaining them in contact with each other for a period of time suflicient to effect the desired reaction between all or substantially all of the hydrogen peroxide with the unsaturated halide present in the reaction zone. In theory, it is necessary or at least desirable to employ equimolecular quantities of hydrogen peroxide and of the mono-olefinic molecule of the hydrogen peroxide reacts'wi -a molecule of the mono-oleflnic halide and by ox- 'ylates thelatterto produce the desired dihydroxylated halogenated organic compound. In

practice it was found that it is generally preferable to employ the unsaturated halide in a quantity in excess of that which will react with all of the hydrogen peroxide present in the reaction zone. If a poly-olefinic allyl type halide is to be hydroxylated in accordance with the present process, and if it is desired to saturate all of the double bonds, it will naturally be necessary to employ greater quantities of the hydrogen peroxide.

The reaction may be effected at atmospheric pressures, although higher or lower pressures may .also be used. As to the temperatures, it is pre-' ferred to employ temperatures in the range of between about 0 C. and about 50 C. However, lower and higher temperatures may also be employed. It is to be noted, nevertheless, that temperatures very much above 50" 0. should be gen'- erally avoided since such high temperatures tend to effect the oxidation rather than the hydroxylation of the unsaturated halide treated.

The hydroxylation according to the process of this invention may be effected batchwise, intermittently or in a continuous manner. In cases of batch production of the polyhydroxylated halogenated compounds, the given unsaturated halide of the defined class may be mixed with the hydrogen peroxide and allowed to stand in the'presence of the catalyst (e. g. osmium tetroxide) for a period of time suiiicient to allow the reaction of the halide with all of the hydrogen. peroxide present. If the reaction is to be eifected in an aqueous medium, the hydrogen peroxide may first be dissolved in water, and the solution thus formed may then be mixed with the halide to which the catalyst has been added. The result-' ant reaction mixture may then be treated by any of the known methods to recover the halogenated polyhydroxylated compound. For instance, when allyl chloride is reacted with hydrogen peroxide in an aqueous medium and in the presence of osmium tetroxide, the gylcerol monochlorhydrin (CH2C1CHOHCH2OH) which is soluble in water, will be found in the aqueous phase, whereas the excess allyl chloride will remain in the nonaqueous or oil phase. The two phases may then be separated, and the may then be recovered in an anhydrous state, example by a distillation under vacuum.

The process is also adaptable to the continuous hydroxylation of the defined class of unsaturated halides. For this purpose, the reactants, whether in the presence or absence of water, and/or whether in the presence or absence .of a solvent for the resultant polyhydroxylated halogenated compound, may be continuously conveyed through a reaction zone wherein these reactants are mainfor tained in a state of agitation to obtain intimate glycerol monochlorhydrin ample in water,

. 300 C. to 500 action mixtures containing, inter alia, various percentages of hydrogen peroxide and of organic highly advantageous. agitate the reactants violently during-the hydroxylation step. e gnstead of employin pure hydrogen peroxide (whether as such or as a solution thereof; for exether, etc.), it is also. to use. mixtures which contain hydrogen peroxide. or substances or mixtures. of substances which readily yield hydrogen peroxide under the operate conditions. For example, producis of the non explosive incomplete oxidation of saturated aliphatic and/or alicyclic hydrocarbons, such as and the like, with propane, butane, cyclopropane, oxygen, particularly when effected for relatively short periods of time and at temperatures of horn 0., result in the formation of reperoxides. These latter frequently yield hydrogen peroxide under the"defined hydromlafing conditions, thus increasing the active oxygen content of the liquid reaction product and rendering it highly suitable as a substitute for pure hydrogen peromde in the process constituting the object of the present invention. compounds which maybe used in lieu of'hydrogen peroxide consists of the double or complex compounds of hydrogen peroxide with other substances, these compounds also being able to yield hydrogen peroxide under the operating conditions. Complex compounds of hydrogen peroxide with urea'are examples of this class. Also, inorganic peroxygenated compounds, such as persuliuric acid, ammonium persuliate, etc., which yield hydrogen peroxide for'example by hydrolysis, may also be used in lieu of or with pure hydrogen peroxide. Therefore, the term hydrogen peroxide as employed herein and in the appended claims, includes not only pure hydrogen peroxide but also mixtures containing hydrogen peroxide and/or compounds which will yield hydrogen peroxide under the operating conditions specified herein.

The. following examples are introduced for the purpose of illustrating preferred embodiments oi the process of the present invention, it being understood that the invention is not to be restricted to the specific conditions described the examples.

Example f Approximately 20 cc. of a 33% aqueous hydrogen peroxide solution was first diluted with about 180 cc. of water, and the aqueous solution thus formed was then intimately mixed at about 28 C. with approximately 22.5 grams of allyl chloride and 15 milligrams of osmium tetroxide. The allyl chloride was thus used in a 50% excessover the amount which can be hydrowlated by the hydrogen peroxide present. The mixture was allowed to stand for about 3 days. At the end of this period of time the mixture was decanted and the aqueous phase was separately distilled under a reduced pressure to recover the water as an overhead fraction. The remaining bottom free on, which weighed 16.7 grams, had a boiling range of between about 115 C. and 120 C. at 13 mm. of mercury pressure. .An analysis otthis product showed that it was pure glycerol monocblorhydrin, which was thus 77% based on the quantity of the mouochlorhydrin which could have produced by the addition of allof the hydrogen peroxide to the allyl chloride.

seas ns .scdmpze rrv Approximately'18L8 cc. of a liquid produced by an incomplete combustion of propane andcontainlng about 21 milligram equivalents of active cubic centimeter of the liquid, wasadded to about 18 grams of allyl chloride which I oxygen per 1 contained approximately 5 milligrams of osmium 'atthe end of was found to .be substantially free from any active'oxygen. The mixture was then decanted,

and the aqueous layer was separated and then detetroxide dissolved therein. 'The mixture. thus produced was continuously agitated for 3 days which period of time the mixture hydrated by subjecting it to vacuum distillation. The residual fraction thus formed weighed about 9.6 grams and consisted of glycerol monochlorhydrin having a' boiling range of between 116 C.

and 121 C. at 'millimeters of mercury pres-'- Another class of sure. The yield was therefore 44% based on the available hydrogen peroxide.

Example III About 20 ccQof a 33% aqueous hydrogen peroxide solution was first diluted with about 180 cc.-

ol water and then thoroughly mixed with about 21.5 grams of methallyl' chloride to which about 1.6 milligrams of osmium tetroxide was previously I added. The methallyl chloride was thus employed in a quantity which was 20% in excess of that which can be hydroxylated-by the hydrogenperoxide present in the mixture. After standin for a period of 3 days at a temperature of about 29 C. to 25 C., the mixture was found'to be free from any hydrogen peroxide. The aqueous phase was then separated and subjected to vacuum distillation to drive off all of the water. The remaining residue weighed about ll'grams, had a boiling temperature range of between about 104 C. and 109 C. at 13 mm. of mercury pressure, and upon analysisv was found to be substantially pure beta-methyl glycerol monochlorhydrin. The yield was thus equal to about 45%" of the theoretical.

Although the examples describe the invention with particular reference to the catalytic hy-' droxylation of allyl chloride in the presence of osmium tetroxide, it is to be understood thatit is possible to employ other hydroxylating catalysts as well as other unsaturated halides of the class described above. The reaction according to the process of the present invention yields halo- I genated po hydroxylated organic compounds which are va uable chemicals and may be used as such or as intermediates in the manufacture of other useful and valuable compounds. For ex 1 ample, the resulting halogenated po hydroxylated compounds, and particularly the monohalogenated dihydroxylated organic compounds, may

be used as solvents and/or refining or extractin agents. Also, they may be employed as intermediates in the production of various valuable Y epoxides, hydroxy 'epoxides, .glycidols. lycerols.

esters, ethers, ether esters, oxy-aldehydes, oxycarboxylic acids, and the like.

. Iclaim as my invention:

l. A process for producing and recovering glycerol monocblorhydrln which comprises react-.

ing allyl chloride with hydrogen peroxide at a temperature of between about 0 C. and about 50 C. in the presence of osmium tetroxide and I of a substantial amount of water to produce a reaction mixture containing an aqueous solution of glycerol 'monochlorhydrin; separating the aqueous phase and recovering glycerol monochlorhydrin therefrom. v

2. A process for producing glycerol monochlorhydrin which comprises reacting allyl chloride with hydrogen peroxide at a temperature or between about C. and about 50 C., in the presence of osmium tetroxide and of a substantial amount 01' water, and recovering glycerol monochlorhydrin from the reaction mixture. I

3. A process for producing ycerol monochlorhydrin which comprises reacting allyl chloride with hydrogen peroxide in the presence or a catalytlcally active oxide 0! a metal selected from the group consisting of ruthenium, vanadium, chromium, molybdenum and osmium, and in the presence of a substantial amount oi water.

4. A process for producing glycerol monohalohydrins which comprises reacting an allyl halide with hydrogen peroxide at a temperature oi! between about 0 C. and 50 C. and in the presence oi osmium tetroxide and of a substantial amount of water.

5. A process for producing glycerol monohalohydrins which comprises reacting an ally] halide with hydrogen peroxide in the presence of .osmium tetroxide and of a substantial amount of water.

6. A processfor producing glycerol monohalohydrins which comprises reacting an allyl halide with hydrogen peroxide in the presence of a substantial amount of water and 01' an oxide of a metal selected from the group consisting of ruthenium, vanadium, chromium, molybdenum and osmium.

7. A process for producing dihydroxylated halogenated compounds which comprises reacting a mono-oleflnic monohalide having the halogen atom in allyl position with respect to the double bond with hydrogen peroxide in the presence of a catalytically active oxide of a metal selected from the group consistingoi ruthenium. vanadium, chromium, molybdenum and osmium, and in the presence of a substantial amount or water.

8. A process for producing polyhydroxyiated halogenated compounds which comprises reacting an olefinic monohalide having the halogen atom on a saturated carbon atom directly attached to one of the unsaturated carbon atoms with hydrogen peroxide inthe presence 01 an oxide of a metal selected from the group consisting of ruthenium. vanadium, chromium. molybdenum and osmium, and in the presence 01 a substantial amount of water.

9. A process for producing polyhydroxylated halo compounds which comprises reacting halogenated unsaturated hydrocarbons containing an unsaturated linkage between two aliphatic carbon atoms devoid of halogen atoms with hydrogen peroxide in the presence or osmium tetroxide and of a substantial amount 01' water.

10. The process according to claim 9, wherein the reaction is elected at a temperature of between about 0," C. and about C.

11. A process for producing polyhydroxylated halo compounds which comprises reacting halogenated unsaturated hydrocarbons containing an unsaturated linkage between two aliphatic carbon atoms devoid of halogen atoms with hydrogen peroxide in the presence of an oxide of a metal selected from the group consisting of ruthenium, vanadium, chromium, molybdenum and osmium, in the presence or a substantial amount oi we r.

12. A process for producing and recovering beta-methyl glycerol monochlorhydrin which comprises reacting methallyl chloride with an aqueous solution of hydrogen peroxide at a temperature of between about 0 C. and about 50 C.

in the presence of osmium tetroxide to produce a reaction mixture containing beta-methyl gly-' cerol monochlorhydrin, and recovering said monochlorhydrin from the reaction mixture.

13. A process for producing beta-methyl glycerol monochlorhydrin which comprises reacting methallyl chloride with hydrogen peroxide in the presence of a substantial amount 01'. water and'of an oxide 01' a metal selected from the group consisting of ruthenium, vanadium, chromium, molybdenum and osmium.

14. A process for producing beta-methyl glycerol monohalohydrin which comprises reacting a methallyl halide with hydrogen peroxide in the presence of a substantial amount of water and of an oxide of a metal selected from the group consisting of ruthenium vanadium, chromium,

molybdenum and osmium.

LUDWIG ROSENS'I'EIN. 

